Hydroquinonylsulfonyl azo dye developers



United States Patent 3,218,312 HYDROQUINONYLSULFONYL AZO DYE DEVELOPERSMilton Green, Newton Center, Mass, assignor to Polaroid Corporation,Cambridge, Mass., a corporation of Delaware No Drawing. Filed Oct. 12,1962, Ser. No. 230,288 3 Claims. (Cl. 260-162) This application is inpart a continuation of my copending application, Serial No. 680,434,filed August 26, 1957, now abandoned.

This invention relates to photography and more particularly to products,compositions and processes for the development of photosensitive silverhalide elements.

It is one object of the present invention to provide novel processes andcompositions for the development of silver halide emulsions, in whichcolored developing agents are used to develop a latent image.

Another object is to provide novel processes and compositions for thedevelopment of silver halide emulsions, in which the novel developingagent is capable of developing a latent image and imparting a reversedor positive colored image of said latent image to a super-posedimage-receiving material.

A further object is to provide novel products, processes andcompositions suitable for use in preparing monochromatic andmultichromatic photographic images.

Other objects of the invention will in part be obvious and will in partappear hereinafter.

The invention accordingly comprises the processes involving the severalsteps and the relation and order of one or more of such steps withrespect to each of the others, and the products and compositionspossessing the features, properties and the relation of elements whichare exemplified in the following detailed disclosure, and the scope ofthe application of which will be indicated in the claims.

The novel photographic developing agents employed in this inventionpossess the properties of both a dye and a developing agent; thus theymay be referred to as dye developers. The nature of these dye developerswill be described hereinafter.

The photographic processes and compositions disclosed herein areparticularly useful in the treatment of an exposed silver halideemulsion, whereby a positive dye image may be imparted to anotherelement, herein referred to as an image-carrying or image-receivingelement.

U.S. Patent No. 2,983,606, issued May 9, 1961 to Howard G. Rogers,discloses diffusion transfer processes wherein a photographic negativematerial, such as a photographic element comprising an exposed silverhalide emulsion is developed in the presence of a dye developer toimpart to an image-receiving layer a reversed or positive dye image ofthe developed image by permeating into said emulsion layer a suitableliquid processing composition and bringing said emulsion layer intosuperposed relationship with an appropriate image-receiving layer.

It is an object of this invention to provide additional dyedevelopers'suitable for use in such processes.

In carrying out the process of this invention, a photosensitive elementcontaining a silver halide emulsion is exposed and wetted with a liquidprocessing composition, for example, by immersing, coating, spraying,flowing, etc., in the dark, and the photosensitive element superposed,prior to, during or after wetting, on an imagereceiving element. In apreferred embodiment, the photosensitive element contains a layer of dyedeveloper, and the liquid processing composition is applied to thephotosensitive element in a uniform layer as the photosensitive elementis brought into superposed position with an image-receiving element. Theliquid processing composition permeates the emulsion to provide asolution of dye developer substantially uniformly distributed therein.As the exposed silver halide emulsion is developed, the oxidationproduct of the dye developer is immobilized or precipitated in situ withthe developed silver, thereby providing an imagewise distribution ofunoxidized dye developer dissolved in the liquid processing composition.This immobilization is apparently, at least in part, due to a change inthe solubility characteristics of the dye developer upon oxidation, andespecially as regards its solubility in alkaline solutions. It also maybe due, in part, to a tanning effect on the emulsion by the oxidizeddeveloping agent. At least part of this imagewise distribu tion ofunoxidized dye developer is transferred, by imbibition, to a superposedimage-receiving layer. Under certain circumstances, the layer of theliquid processing composition may be utilized as the image-receivinglayer. The image-receiving layer receives a depthwise diffusion, fromthe emulsion, of unoxidized dye developer, without appreciablydisturbing the imagewise distribution thereof, to provide a reversed orpositive, colored image of the developed image. The image-receivingelement may contain agents adapted to mordant or otherwise fix the diffused, unoxidized dye developer. If the color of the diffused dyedeveloper is atfected by changes in the pH of the image-receivingelement, this pH may be adjusted in accordance with well-knowntechniques to provide a pH affording the desired color. Imbibitionperiods of approximately one minute have been found to give goodresults, but this contact period may be adjusted where necessary tocompensate for variations in temperature or other conditions. Thedesired positive image is revealed by stripping the image-receivingelement from the photosensitive element at the end of the imbibitionperiod.

The dye developers of this invention may be utilized in thephotosensitive element, for example in, on or behind the silver halideemulsion, or they may be utilized in the image-receiving element or inthe liquid processing composition. In a preferred embodiment, a coatingor layer of the dye developer is placed behind the silver halideemulsion, i.e., on the side of the emulsion adapted to be located mostdistant from the photographed subject when the emulsion is exposed andpreferably also adapted to be most distant from the image-receivingelement when in superposed relationship therewith. Placing the dyedeveloper behind the emulsion layer, as in the preferred embodiment, hasthe advantage of providing increased contrast in the positive image, andalso minimizes any lightfiltering action by the colored dye developer.In this preferred embodiment, the layer of dye developer may be appliedby using a coating solution containing about 0.5 to 8%, by weight, ofthe dye developer. Similar concentrations may be used if the dyedeveloper is utilized as a component of the liquid processingcomposition. In an especially useful mode of dispersing the dyedevelopers in the photosensitive elements, the dye developer isdissolved in a water-immiscible solvent and then dispersed in a gelatincoating solution.

The liquid processing composition above referred to comprises at leastan aqueous solution of an alkaline compound, for example, diethylamine,sodium hydroxide or sodium carbonate, and may contain the dye developer.In some instances, it may contain a minor amount of a con ventionaldeveloping agent. If the liquid processing composition is to be appliedto the emulsion by being spread thereon, preferably in a relativelythin, uniform layer, it may also include a viscosity-increasing compoundconstituting the film-forming material of the type which, when saidcomposition is spread and dried, will form a relatively firm andrelatively stable film. A preferred filmdroxyl groups.

forming material is a high molecular weight polymer such as a polymeric,water-soluble ether inert to an alkali solution, as, for example, ahydroxyethyl cellulose or sodium carboxymethyl cellulose. Otherfilm-forming materials or thickening agents whose ability to increaseviscosity is substantially unaife-cted when left in solution for a longperiod of time may also be used.

The novel dye developers of this invention may be represented by theformula:

wherein Ar is an aryl nucleus, such as a benzene or naphthalene nucleus;each Z is an alkoxy group, an alkyl I group, preferably a lower alkylgroup such as methyl or ethyl, or a halogen such as chlorine; in is O'or1; u is 0, 1, 2 or 3; v is 0, 1 or 2; p is l or 2; Y is ap-dihydroxyphenyl, or a p-bis-acyloxyphenyl group; and X and X are eachthe radical of an azo coupling component, which coupling component maybe the same or different.

In a preferred embodmient the aryl nucleus is a benzene nucleus, andsuch dye developers may be represented by the formula:

As illustrations of suitable azo coupling components or couplers fromwhich X and X may be derived, mention may be made of phenols andaromatic amines having a free position ortho or para to the hydroxyl oramino group, e. g., phenol, anilines, naphthols, anthrols,naphthylamines, etc.; heterocyclic aromatic compounds containinghydroxyl or amino groups, such as pyrazolones or pyr- :roles; aliphaticor alicyclic activated methylene couplers,

i.e., compounds having an aliphatic or alicyclic methylene groupactivated by two adjacent keto, aldehyde, ester or nitrile groups, whichmay be the same or different, or a keto, aldehyde, ester or nitrilegroup in combination with an amide group, e.g., 1,3-diketones orB-ketonic acid arylamides; etc., and substituted derivatives thereof.Examples of groups which may be present in such substituted derivativesinclude alkyl, sulfo, alkoxy, aryl, aryloxy, amino, keto, alkylamino,arylamino, hydroxyl, cyano, alkylarnido, arylamido, carbalkoxy,carboxamido, sulfonamido, etc.

As used herein with reference to X and X the expression radical of aphenolic coupler is intended to refer to hydroxyphenyl, hydroxynaphthyl,hydroxyanthryl, etc.

( Zn Zv i-S O r-1ir- (N=NX a) m NH2 wherein Y, Z, m, u, v and X have thesame meaning as above, and coupling the diazotized compound (C) into thedesired coupling components providing X The compounds of Formula C,wherein m is 0, e.g., paminophenylsulfonyl-hydroquinone, may be preparedaccording to the procedure of Burton and Hogsarth, JACS 1945, page 468.The hydroxyl groups may be protected during the diazotization andcoupling reactions by the use of protective derivatives, e.g., acylgroups, of said hy- Such acylated compounds may be prewherein Y, Z, a,v, m, p, X, and X have the same meaning as above.

pared according to the procedure disclosed and claimed in US. Patent No.3,019,254, issued January 30, 1962 to to Milton Green and Helen P.Husek. The monoazo intermediates may be made as disclosed herein and maybe employed with-out removal of such protective groups in subsequentdiazotization and coupling steps.

The preferred compound Within the group represented by Formula C is:

-s mQ-avrn The coupling is generally performed at a pH which ispreferably not greater than about 9. The hydroxy groups of Y areprotected during diazotization and coupling, as by the use of abis-acyloxy derivative as mentioned above.

By the use of two moles of the diazonium salt to each mole of thecoupling component, one may couple twice into certain of the couplingcomponents which provide the radical X as, for example, phenols andaromatic amines which have two directing groups and two free couplingpositions, such as 1,6-dihydroxy naphthalene and 1,5-diaminonaphthalene.

Where the coupling component is a phenolic coupler, and particularly anaphthol, it has been found that coupling ortho to the hydroxyl groupgives a dye developer of superior color properties.

As examples of suitable dye developers within the scope of thisinvention, mention may be made of the followmg:

1-pheny1-3-methyl-4- [phydroquinonylsulfonyl) pheny1azo1-5-pyrazolone OH O H 'diazotizable amino group, e.g., a nitro group. The diazotizableamino group may be on a nucleus other than the one substituted by theazo grouping.

As examples of additional coupling componentswhich may be used toprovide X mention may be made of:

4-benzyl-1-naphthol 4-methyl-1-naphthol 4-methoxy-u-naphthylamine4-acetamido-a-naphthylamine Phenol Aniline 1,5-naphthalenediaminep-Cresol l-hydroxyanthracene 1-hydroxy-2-naphthanilide DiketohydrindeneMalononitrile Acetoacetanilide.

The novel dye developers within the scope of this invention givesgenerally brighter dye images in the diffusion transfer process thanmany other azo dye developers. This unobvious property may beillustrated by the compound of Formula II which compound is a brighterdye than 2- [p- 2,5 '-dihydroxyphenethyl -phenylazo] 4-methoxy-l-naphthol employing the same azo coupler, disclosed and claimedin the copending application of Elkan R. Blout, Milton Green and HowardG. Rogers, Serial No. 144,816, filed October 18, 1961, now U.S. PatentNo. 3,134,672, and also fades to a magenta shade that is brighter thanthe shade of the above-mentioned 2-[p-(2,5'-dihydroxyphenethyl)-phenylazo] 4 methoxy 1- naphthol after bothdyes have been exposed to accelerated fading conditions for an equalperiod. It should also be noted that the muddy or dull appearancefrequently found in dye developers such as the above-identified 2-[p-(2, -dihydroxyphenethyl)-phenylazo] 4 methoxyl-naphthol after suchaccelerated fading tests is not found in the dye developers of thisinvention. In other words, the dye developer of Formula II fades toshades of magenta without the appearance of undesirable dull colorcharacteristics which may be described as muddying, but rather retainsthe brightness characteristics originally found in the dye beforefading.

The dye developers of this invention are pH sensitive since the sulfonyllinking group is not an insulating group and therefore care must betaken in the utilization of such dye developers to provide a pH whichwill afford the desired color.

The dye developers of this invention are less active dye developersthan, for example, the dye developers of the above-mentioned applicationSerial No. 144,816, and are therefore useful where such a diminisheddegree of activity is desired.

The following examples of the preparation of dye developers within thescope of this invention by diazotizing and coupling compounds withinFormula C are given for the purposes of illustration only.

Example 1 2.9 g. of p-aminophenylsulfonyl-hydroquinone-0,0'-diacetate(0.0083 mol) is dissolved in 20 cc. of water and 25 cc. of glacialacetic acid by heating. The mixture is cooled to about C. and 0.66 cc.of 12.5 N hydrochloric acid (0.0083 mol) is added. The resultant mixtureis cooled in an ice bath and diazotized with sodium nitrite. Theresulting diazo slurry is added, with constant stirring, to a mixture of1.4 g. of 1-phenyl-3-methyl-5- pyrazolone (0.008 mol), 20 cc. ofpyridine, 50 cc. of water, and 20 cc. of saturated sodium bicarbonatesolution, concurrently with suflficient 10% sodium carbonate solution tomaintain a pH of 7 to 8. The resulting slurry is stirred for about 2hours at room temperature, filtered and washed with water. The acetylgroups are removed by hydrolysis in vacuo with 3 g. of 85% potassiumhydroxide, 10 cc. of water, 40 cc. of ethanol and heating for a fewminutes on a steam bath. The resulting mixture is cooled, poured into adilute hydrochloric acid solution and then filtered. The precipitate ispurified by dissolving it in methyl Cellosolve and reprecipitating witha 1% hydrochloric acid solution to yield 1.4 g. of l-phenyl-3-methyl-4-[p-(hydroquinonylsulfonyl) phenylazo] 5- pyrazolone [FormulaI], M.P. 235 to 237 C. The absorption spectrum of this product exhibitsa k ax of 390 m in acetone, e=27,000'.

Example 2 4 g. of p-aminophenylsulfonyl-hydroquinone-0,0-diacetate(0.0115 mol) is dissolved in 30 cc. of glacial acetic acid and 0.92 cc.of 12.5 N hydrochloric acid by heating to a boil. The mixture is cooledin an ice bath and diazotized with sodium nitrite. The resultant cleardiazo solution is added to 30 cc. of an ice water mixture and theresultant diazo slurry is added with constant stirring, to a mixture of1.4 g. of 4-methoxy-1-naphthol (0.008 mol), 70 cc. of acetone, 40 cc. ofsaturated sodium bicarbonate solution, 20 cc. of pyridine, and 40 cc. ofwater, concurrently with sufficient 10% sodium carbonate to maintain apH of 7 to 8. The resulting slurry is stirred for about 2 hours at roomtemperature, diluted with water and the mixture decanted yielding a gumproduct. The acetyl groups are removed by hydrolysis in vacuo with 4 g.of 85% potassium hydroxide, cc. of ethanol, 15 cc. of water and heatingfor a few minutes on a steam bath. The resulting mixture is cooled,poured into a dilute hydrochloric acid solution and then filtered. Theresulting precipitate is purified by dissolving it in a methylCellosolve solution and reprecipitating with water to yield 1.1 g. of4-methoxy-2-[p-(hydroquinonylsulfonyl)-phenylazo]-1-naphthol [FormulaII), M.P. 184 to 188 C. The absorption spectrum of this product exhibitsa k of 516 mu in acetone, e=20,500.

In the following examples all parts are given by weight except whereotherwise noted,.and all operations involving light-sensitive materialsare carried out in the absence of actinic radiation. These examples areintended to be illustrative only of the photographic use of the dyedevelopers and should not be construed as limiting the invention in anyway.

Example 3 A photosensitive element is prepared by coating agelatin-coated film base with a solution containing 3% of1-phenyl-3-methyl-4- [p- (hydroquinonylsulfonyl)-phenylazo]-5-pyrazolone [Formula I as prepared in Example 1], in a 4%solution of cellulose acetate hydrogen phthalate in a 50:50 mixture, byvolume, of acetone and tetrahydrofuran. After this coating has dried, asilver iodobromide emulsion is applied.

This photosensitive element is exposed and processed by spreading anaqueous liquid processing composition comprising:

Percent Sodium carboxymethyl cellulose 6.0 1-phenyl-3-pyrazolidone 0.2Sodium hydroxide a 5.0 Potassium bromide 0.5

between said photosensitive element and an image-receiving element assaid elements are brought into superposed relationship. Theimage-receiving element comprises a cellulose-coated baryta paper whichhas been coated with a solution comprising 10% Nylon Type F8 (trade namefor N-methoxymethyl polyhexamethylene adipamide) in 80% aqueousisopropanol. After an imbi'bition period of approximately one minute,the image receiving element is separated and contains a yellow positivedye image of the photographed subject.

Exwmple 4 A photosensitive element is prepared similar to that describedin Example 3 using 3% of 4-methoxy-2-[p-(hydroquinonylsulfonyl)-phenylazo]-1-naphthol [Formula II as prepared inExample 2]. Exposure and processing with a liquid processing compositionand image-receiving element similar to those described in Example 3 givea magenta positive dye image.

The dye developers of this invention are also useful in integralmultilayer photosensitive elements for use in multicolor diffusiontransfer processes. As an example of such photosensitive elements,mention may be made of the photosensitive elements disclosed and claimedin the copending US application of Edwin H. Land and Howard G. Rogers,Serial No. 565,135, filed February 13, 1956, wherein at least twoselectively sensi tized photosensitive strata are superposed on a singlesupport and are processed, simultaneously and without separation, with asingle common image-receiving element. A suitable arrangement of thistype comprises a support carrying a red-sensitive silver halide emulsionstratum, a green-sensitive silver halide emulsion stratum and ablue-sensitive silver halide emulsion stratum, said emulsions havingassociated therewith, respectively, a cyan dye developer, a magenta dyedeveloper and a yellow dye developer. In one of the preferredembodiments of photosensitive elements of this type, the dye developersare disposed in separate alkali-permeable layers behind thephotosensitive silver halide emulsion stratum with which they areassociated.

The photosensitive elements within the scope of this invention may beused in roll film units which contain a plurality of photosensitiveframes. The photosensitive elements of this invention are especiallyuseful in composite roll film intended for use in a Polaroid LandCamera, or a similar camera structure such, for example, as the cameraforming the subject matter of U.S. Patent No. 2,435,717, issued to EdwinH. Land on February 10, 1948. In general, such composite roll filmscomprise a photosensitive roll, a roll of image-receiving material and aplurality of pods containing an aqueous alkaline processing solution.The rolls and pods are so associated with each other that, uponprocessing, the photosensitive element may be superposed on theimagereceiving element and the pods may be ruptured to spread theaqueous alkaline processing solution between the superposed elements.The nature and construction of the pods used in such units are wellknown to the art. See, for example, U.S. Patents Nos. 2,543,181 and2,634,- 886, issued to Edwin H. Land.

It will be noted that the liquid processing composition may contain oneor more auxiliary or accelerating silver halide developing agents, suchas p-methylaminophenyl (Metol); 2,4-diaminophenol (Amidol);benzylaminophenol; hydroquinone; a substituted hydroquinone such astoluhydroquinone, phenylhydroquinone, or 4'-methylphenylhydroquinone; ora 3-pyrazolidone such as 1-phenyl-3-pyrazolidone. These silver halidedeveloping agents are substantially colorless, at least in theirunoxidized form. It is possible that some of the dye developer oxidizedin exposed areas may be oxidized by an energy transfer reaction withoxidized auxiliary developing agent.

In addition, development may be effected in the presence of an oniumcompound, particularly a quaternary ammonium compound, in accordancewith the processes dis-closed and claimed in the copending applicationof Milton Green and Howard G. Rogers, Serial No. 50,851, filed August22, 1960.

The dye developers of this invention may be used also in conventionalphotographic processes, such as tray or tank development of conventionalphotosensitive films, plates or papers to obtain black and white,monochromatic or toned prints or negatives. By way of example, a

developer composition suitable for such use may comwashing medium orother medium in which the unreacted dye developer is soluble. Theexpression toned is used to designate photographic images wherein thesilver is retained with the precipitated dye, whereas monochromatic isintended to designate dye images free of silver.

It should be noted that the dye developers of this medium areself-sufficient to provide the desired color image and do not dependupon coupling reactions to produce the desired color. They thus providea complete departure from conventional photographic color processes inwhich the color is produced by a coupling reaction between a colorformer or coupler and the oxidized developing agent, as well asso-called auto-coupling processes in which color is obtained by areaction of the oxidized developing agent with unoxidized developingagent.

It will be apparent that, by appropriate selectionof the image-receivingelement from among suitable known opaque and transparent materials, itis possible to obtain either a colored positive reflection print or acolored positive transparency. Likewise, the inventive concepts hereinset forth are adaptable for multicolor work by theme of specialphotographic materials, for example, film materials of the typecontaining two or more photosensitized elements associated with anappropriate number of imagereceiving elements and adapted to be treatedwith one or more liquid processing compositions, appropriate dyedevelopers suitable to impart the desired subtractive colors beingincorporated in the photosensitized elements or in the liquid processingcompositions. Examples of such photographic materials are disclosed inU.S. Patent No. 2,647,049 to Edwin H. Land.

As examples of useful image-receiving materials, mention may be made ofnylon, e.g., N-rnethoxymethylpolyhexamethylene adipamide, polyvinylalcohol, and gelatin, particularly polyvinyl alcohol or gelatincontaining a dye mordant such as poly-4-vinylpyridine. Theimage-receiving element also may contain a development restrainer, e.g.,l-phenyl-S-mercaptotetrazole, as disclosed in the copending applicationof HowardG. Rogers and Harriet W. Lutes, Serial No. 50,849, filed August22, 1960.

The dye developers herein set forth are also useful in the formation ofcolored images in accordance with the photographic products andprocesses described and claimed in U.S. Patent No. 2,968,554, issued toEdwin H. Land on January 17, 1961.

The novel compounds herein disclosed are also suitable for use as dyesfor textile fibres, such as nylon.

In the preceding portions of the specification the expression color hasbeen frequently used. This expression is intended to include the use ofa plurality of colors to obtain black.

My copending U.S. application, Serial No. 230,287, filed concurrentlyherewith, claims the photographic utilization of the novel compounds ofthe present invention.

Since certain changes may be made in the above products, compositionsand processes without departing from the scope of the invention hereininvolved, it is intended that all matter contained in the abovedescription shall be interpreted as illustrative and not in a limitingsense.

What is claimed is:

1. A compound of the formula:

wherein Ar is an aryl nucleus selected from the group consisting ofbenzene and naphthalene nuclei; each Z is selected from the groupconsisting of chlorine and lower alkyl; w is aninteger from 0 to 3,inclusive; v is an integer from 0 to 2, inclusive; p is an integer from1 to 2, inclusive; Y is a p-dihydroxyphenyl radical; and X, is theradical of an azo dye coupler linked to said -N=N- group.

2.. 1-phenyl-3-methyl 4 [p-(hydroquinonylsulfonyl)-phenylazo1-5-pyrazolone.

3. 4-methoxy 2 [p-(hydroquinonylsulfonyl)-phenylazo]-l-naphthol.

References Cited by the Examiner UNITED STATES PATENTS 2,773,863 12/1956Bolliger 260-162 2,776,959 1/1957 Frisch 260-162 2,993,886 7/1961 Weiset al. 260l63 2,997,390 8/1961 Land 260-29D OTHER REFERENCESVenkataraman: The Chem. of Synthetic Dyes, volume 1 (pages 358 and 359)(1952).

9 CHARLES B. PARKER, Primary Examiner.

1. A COMPOUND OF THE FORMULA: